WO2022225066A1 - Air electrode having hydrogen peroxide-containing electric double layer, and metal-air battery using same - Google Patents

Air electrode having hydrogen peroxide-containing electric double layer, and metal-air battery using same Download PDF

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WO2022225066A1
WO2022225066A1 PCT/JP2022/018775 JP2022018775W WO2022225066A1 WO 2022225066 A1 WO2022225066 A1 WO 2022225066A1 JP 2022018775 W JP2022018775 W JP 2022018775W WO 2022225066 A1 WO2022225066 A1 WO 2022225066A1
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electrode
metal
hydrogen peroxide
air
copper
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PCT/JP2022/018775
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French (fr)
Japanese (ja)
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光廣 佐想
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光廣 佐想
クロステクノロジーラボ株式会社
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Priority to CA3216113A priority Critical patent/CA3216113A1/en
Priority to KR1020237039973A priority patent/KR20240027580A/en
Priority to JP2023515544A priority patent/JPWO2022225066A1/ja
Priority to AU2022261634A priority patent/AU2022261634A1/en
Priority to EP22791837.2A priority patent/EP4329049A1/en
Publication of WO2022225066A1 publication Critical patent/WO2022225066A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/08—Structural combinations, e.g. assembly or connection, of hybrid or EDL capacitors with other electric components, at least one hybrid or EDL capacitor being the main component
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/12—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with flat electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an air electrode provided with an electric double layer containing hydrogen peroxide and a metal-air battery using the same.
  • Hydrogen fuel cells and metal-air batteries are known as fuel cells, but hydrogen fuel cells require compressed hydrogen to supply hydrogen, and in the case of use in automobiles, there are difficulties in supplying and storing the compressed air. Therefore, it has been proposed to use hydrogen peroxide as a fuel.
  • metal-air batteries a carbon electrode is generally used as the air electrode. is generally used and improved (Patent Document 1).
  • a conductive polymer poly(3,4-ethylenedioxythiophene (PEDOT), is used as the cathode electrode instead of the carbon electrode, while a nickel mesh is used as the anode electrode.
  • PEDOT poly(3,4-ethylenedioxythiophene
  • Non-Patent Document 1 A fuel cell that exhibits an open-circuit potential in the range of 0.5 to 0.6 V at a power density of 0.20 to 0.30 mW cm has been announced (Non-Patent Document 1).
  • CuHCF copper hexacyanoferrate
  • the present inventors found that when hydrogen peroxide is supplied to the alkaline electrolyte of a metal-air battery, the interface between the metal electrode and the electrolyte functions as a separator.
  • a metal electrode is used as the positive electrode in a fuel cell, a disproportionation reaction of hydrogen peroxide occurs and it was said that it could not be used.
  • an electrolytic solution containing hydrogen oxide forms a dipole electric double layer on the copper electrode surface, the copper electrode can be used as an air electrode and hydrogen peroxide can be used as a fuel.
  • the first object of the present invention is to provide an air electrode comprising a copper electrode having an electric double layer containing hydrogen peroxide
  • the second object of the present invention is to provide a copper electrode having an electric double layer containing hydrogen peroxide.
  • An object of the present invention is to provide an air fuel cell as an air electrode.
  • the present invention firstly provides a fuel cell using a neutral or alkaline electrolyte containing at least hydrogen peroxide, in which metal copper or an alloy thereof immersed in the electrolyte is used as a cathode electrode, and peroxide Provided is an air electrode characterized by comprising a dipole electric double layer formed of hydrogen.
  • the present invention includes a neutral or alkaline aqueous electrolyte containing hydrogen peroxide and forming an electric double layer at the interface with the electrode, a cathode electrode made of metallic copper or an alloy thereof immersed in the electrolyte, and a cathode
  • An anode electrode made of a metal or an alloy thereof whose electrode potential is less noble than that of the electrode, and an electrolyte solution containing hydrogen peroxide formed between the interface between the cathode electrode and the electrolyte solution to form a dipole electric double layer
  • a metal-air battery that can be used as an air electrode instead of a carbon electrode is provided.
  • the hydrogen peroxide in the electrolyte is an electric dipole (dipole), it is oriented on the electrode surface to form a dipole electric double layer.
  • 4A and 4B are functional explanatory diagrams thereof.
  • an electric double layer is usually formed at the interface between the electrodes and the electrolyte. is additionally added, it functions as a dipole to form a dipole electric double layer.
  • One of the factors is the function of hydrogen peroxide as a dipole.
  • a dipole electric double layer is formed at the interface with the electrode surface by the arrangement of electric dipoles (dipoles).
  • the oxidizing power of hydrogen peroxide also cooperates, and according to the present invention, hydrogen peroxide is the cause of the inferior ionization progress rate of the positive electrode on the cathode side compared to the negative electrode on the anode side, which is the bottleneck of the metal-air battery.
  • hydrogen peroxide is the cause of the inferior ionization progress rate of the positive electrode on the cathode side compared to the negative electrode on the anode side, which is the bottleneck of the metal-air battery.
  • the addition of hydrogen peroxide is different from the action of a depolarizer that avoids the effects of hydrogen ions in a voltaic battery with an acidic electrolyte
  • the hydrogen peroxide added to the electrolyte is
  • the copper cathode has a catalytic function as an air electrode, and various power generation reactions are exhibited on the surface of the copper cathode electrode.
  • the anode obtains electrons through an oxidation reaction of 2Mg ⁇ 2Mg 2+ +4e ⁇ , while the cathode electrode reduces oxygen to O 2 +2H 2 O+4e ⁇ ⁇ 4OH ⁇ to form hydroxy ions. It generated and generated electricity, and the amount of current increased when a copper electrode was used as the cathode electrode in a neutral or alkaline electrolyte containing hydrogen peroxide. Looking at this factor, in a battery with such a configuration, not only is the ionization reaction delay, which is a bottleneck in metal-air batteries, eliminated by the addition of hydrogen peroxide, but it is also possible to confirm the generation of oxygen and hydrogen on the cathode side.
  • the hydrogen peroxide decomposes in the fuel cell on the surface of the copper electrode.
  • the cathode H 2 O 2 + 2H ++ 2e ⁇ ⁇ 2H 2 O (1.78 V vs.
  • FIG. 1 is a conceptual diagram showing a metal-air battery of the present invention
  • FIG. FIG. 4 is a perspective view showing a copper cathode electrode with spacers interposed therebetween
  • FIG. 3 is a conceptual side view of a state in which a copper cathode electrode and a magnesium anode electrode are combined
  • 1 is a photograph of copper cathode electrodes forming a number of microcapacitors.
  • FIG. 3B is a schematic side view of a state in which the copper cathode electrode and the magnesium anode electrode of FIG. 3A are combined; BRIEF DESCRIPTION OF THE DRAWINGS FIG.
  • FIG. 1 is a conceptual diagram showing the configuration of the air electrode capacitor of the present invention, in which (A) shows a state in which an electric double layer containing hydrogen peroxide dipoles and a metal oxide is formed on the surfaces of the anode and cathode electrodes; ) shows a state in which an electric double layer containing hydrogen peroxide dipoles and a metal oxide is formed only on the surface of the anode electrode.
  • 1A and 1B are conceptual diagrams showing a configuration having a microcapacitor of the present invention as an electric double layer; FIG.
  • an Al or Mg anode electrode and a Cu cathode electrode are immersed in a neutral or alkaline electrolyte containing hydrogen peroxide and placed opposite each other to form a metal-air battery.
  • Electromotive force in the configuration of anode electrode/alkaline electrolyte containing hydrogen peroxide/cathode electrode, the reaction of the metal-air battery is as follows.
  • the metal oxidation reaction on the anode side is M ⁇ M n + + ne -
  • the oxygen reduction reaction on the cathode side becomes O 2 +H 2 O+4e ⁇ ⁇ 4OH ⁇ .
  • hydrogen peroxide is added to the electrolytic solution in order to promote the reduction reaction on the cathode side of the metal-air battery, thereby improving the cause of the inferior ionization rate of the positive electrode on the cathode side compared to the negative electrode on the anode side.
  • metallic copper dissolves partially in hydrogen peroxide as Cu+2H 2 O 2 ⁇ Cu 2+ +2OH+2OH - and Cu+2OH ⁇ Cu 2+ +2OH - , but Cu 2+ +2HO 2 - ⁇ Cu+2HO 2 and HO 2 groups form the Haber u. Willstatter chain. This is thought to be because the decomposition of hydrogen peroxide is accelerated by (Non-Patent Document 3).
  • FIG. 1 is a conceptual diagram of the metal-air battery of the present invention.
  • an electrolytic solution containing hydrogen peroxide is interposed between the Mg anode electrode, the Cu cathode electrode, and the electrolytic solution, an electric double layer having hydrogen peroxide as a dipole is formed at the interface between the electrolytic solution and the electrode,
  • the electrodes do not short and they work together. function as a capacitor.
  • Hydrogen peroxide forms a dipole electric double layer on the surface of the cathode electrode as a dipole.
  • the anode metal ions are oxidized to form oxides (some of which are metal hydroxides). and B, FIGS. 4A and B).
  • hydrogen peroxide was added to the electrolytic solution as an oxidizing agent for forming an insulating electric double layer on the surface of the cathode electrode.
  • sodium percarbonate is used to supply part or all of the hydrogen peroxide to the aqueous electrolytic solution.
  • a neutral or alkaline aqueous solution containing 0.5 to 2.0 mol of alkali metal or alkaline earth metal halide salt, particularly sodium chloride, and several percent to ten and several percent of hydrogen peroxide water (volume %) or sodium percarbonate (% by weight) is preferably added.
  • the anode electrode and the cathode electrode are alternately arranged to face each other with a constant spacing interposed between them, and an electric double layer capacitor is formed from an aqueous electrolyte solution containing hydrogen peroxide at the contact portion between the anode electrode and the cathode electrode ( 4A and B), the spacer is preferably made of the same metallic copper or copper alloy as the cathode electrode and has point-like projections at regular intervals on the counter electrode surface (FIGS. 5A and B).
  • FIGS. 2A-B and 3A-B were used to compare the performance of cells with and without the microcapacitor concept shown in FIGS. 5A-B.
  • a top-opening cuboid plastic container with a capacity of 3000 ml is used.
  • 5A and B a large number of triangular protrusions 11 with a height of 50 mm were cut vertically and horizontally at intervals of 150 mm to 200 mm on a copper cathode electrode plate 10 having a thickness of 1 mm and a size of 100 mm by 100 mm (photograph FIG. 3A), and FIG. 3B.
  • FIG. 3A photograph FIG. 3A
  • the copper plates 10 at both ends are laminated with the protrusions 11 facing inward, and the copper electrodes 10 are laminated back to back in the middle to sandwich a magnesium anode electrode plate 20 having a thickness of 2 mm and a length and width of 100 ⁇ 100 mm.
  • This combination of electrodes can be used to form a microcapacitor on the surface of the copper cathode electrode, as shown in FIGS. 5A and B.
  • FIG. On the other hand, a copper cathode electrode plate 10 having a thickness of 1 mm and a length and width of 100 ⁇ 100 mm shown in FIG.
  • a Mg anode electrode plate 20 having a thickness of 2 mm and a size of 100 ⁇ 100 mm is sandwiched between the cathode electrode plates with spacers S interposed therebetween.
  • the top end view shown in FIG. 2B is obtained. Using this combination of electrodes does not form the microcapacitor shown in FIGS.
  • an electrolytic solution of 0.5 mol/l or more, preferably 1.5 mol/l or more, 2 mol/l of sodium chloride is prepared in about 1500 ml of pure water, and 50 to 100 g of sodium percarbonate and 30 g of sodium percarbonate are added thereto. 50 ml of % hydrogen peroxide solution is added. After a certain period of time, the cell reaction consumes hydrogen peroxide and the light bulb decreases, so add 10 ml of 30% hydrogen peroxide solution every 2 to 3 hours.
  • the performance of the electrode configuration of FIGS. 2A and B was compared with the electrode configuration of FIGS. 3A and B to compare the performance with and without the microcapacitor formed on the copper cathode electrode surface. Since the conditions were the same except for the electrode configuration, the point that the hydrogen peroxide fuel cell reaction in alkaline electrolyzed water was accompanied by the magnesium air cell reaction was the same.

Abstract

[Problem] To provide an air electrode having a dipole electric double layer containing hydrogen peroxide, and a metal-air battery having the same. [Solution] Provided are: a separator-less battery in which, in a neutral or alkaline electrolyte containing hydrogen peroxide, a cathode electrode of metal copper, a metal anode having a lower electrode potential than copper, and an electric double layer comprising the hydrogen peroxide as a dipole are formed to provide an insulating dipole electric double layer that functions as a separator between the anode electrode and the cathode electrode; and a metal-air battery that uses, as an air electrode, a copper cathode having an electric double layer comprising hydrogen peroxide as a dipole.

Description

過酸化水素を含む電気二重層を備える空気極及びそれを用いる金属空気電池Air electrode provided with electric double layer containing hydrogen peroxide and metal-air battery using the same
　本発明は過酸化水素を含む電気二重層を備える空気極及びそれを用いる金属空気電池に関する。 The present invention relates to an air electrode provided with an electric double layer containing hydrogen peroxide and a metal-air battery using the same.
　燃料電池としては水素燃料電池、金属空気電池が知られているが、水素燃料電池は水素供給減として圧縮水素を必要とし、自動車での使用の場合、その圧縮空気の供給及び貯蔵に難点があるため、燃料として過酸化水素を用いることが提案されている。また、金属空気電池では一般に空気極として炭素電極が使用されているが、負極でのイオン化に比して空気極での酸素のイオン化の進行速度が遅いことが問題となっており、多孔質カーボンを用い、その改良を行うのが一般的である（特許文献１）。また、燃料電池では、炭素電極に代えてカソード電極として伝導性ポリマーであるポリ(3,4-エチレンジオキシチオフェン（PEDOT）を用いる一方、アノード電極としてニッケルメッシュを使用して、不均化反応による損失を発生させることのないように工夫し、0.20～0.30 mW cmの電力密度で0.5～0.6Vの範囲のオープン回路電位を示す燃料電池が発表されている（非特許文献１）。他方、カソード材料としてヘキサシアノ鉄酸銅（ＣｕＨＣＦ）を使用し、アノード材料としてＮｉグリッドを使用する燃料電池も発表されている（非特許文献２）が、金属空気電池の空気極として用いるには汎用性がない。 Hydrogen fuel cells and metal-air batteries are known as fuel cells, but hydrogen fuel cells require compressed hydrogen to supply hydrogen, and in the case of use in automobiles, there are difficulties in supplying and storing the compressed air. Therefore, it has been proposed to use hydrogen peroxide as a fuel. In metal-air batteries, a carbon electrode is generally used as the air electrode. is generally used and improved (Patent Document 1). In fuel cells, a conductive polymer, poly(3,4-ethylenedioxythiophene (PEDOT), is used as the cathode electrode instead of the carbon electrode, while a nickel mesh is used as the anode electrode. A fuel cell that exhibits an open-circuit potential in the range of 0.5 to 0.6 V at a power density of 0.20 to 0.30 mW cm has been announced (Non-Patent Document 1). A fuel cell using copper hexacyanoferrate (CuHCF) as a cathode material and a Ni grid as an anode material has also been announced (Non-Patent Document 2), but it is not versatile enough to be used as the air electrode of a metal-air battery. do not have.
特開２０１４－２２０１０７号JP 2014-220107
　本発明者は、従来技術の空気極の問題点を解決すべく鋭意研究の結果、金属空気電池のアルカリ性電解液中に過酸化水素を供給すると、金属電極と電解液との界面にセパレータ機能を有する双極子電気二重層を形成し、電極の短絡を防止でき、他方、燃料電池では正極として金属電極を使用すると、過酸化水素の不均化反応が起こり、使用できないとされていたが、過酸化水素を含む電解液が銅電極面に双極子電気二重層を形成すると、銅電極を空気極として過酸化水素を燃料として使用することが出来ることを見出した。これらの発見は驚くべきことであった。そこで、本発明は第一に、過酸化水素を含む電気二重層を備える銅電極からなる空気極を提供することを課題とし、第二に、過酸化水素を含む電気二重層を備える銅電極を空気極とする空気燃料電池を提供することを課題とする。 As a result of intensive research aimed at solving the problems of conventional air electrodes, the present inventors found that when hydrogen peroxide is supplied to the alkaline electrolyte of a metal-air battery, the interface between the metal electrode and the electrolyte functions as a separator. On the other hand, when a metal electrode is used as the positive electrode in a fuel cell, a disproportionation reaction of hydrogen peroxide occurs and it was said that it could not be used. It was found that when an electrolytic solution containing hydrogen oxide forms a dipole electric double layer on the copper electrode surface, the copper electrode can be used as an air electrode and hydrogen peroxide can be used as a fuel. These findings were surprising. Therefore, the first object of the present invention is to provide an air electrode comprising a copper electrode having an electric double layer containing hydrogen peroxide, and the second object of the present invention is to provide a copper electrode having an electric double layer containing hydrogen peroxide. An object of the present invention is to provide an air fuel cell as an air electrode.
　すなわち、本発明は、第1に、少なくとも過酸化水素を含む中性又はアルカリ性電解液を用いる燃料電池において、該電解液中に浸漬する金属銅又はその合金をカソード電極とし、その界面に過酸化水素で形成される双極子電気二重層を形成してなる、ことを特徴とする空気極を提供するものである。 That is, the present invention firstly provides a fuel cell using a neutral or alkaline electrolyte containing at least hydrogen peroxide, in which metal copper or an alloy thereof immersed in the electrolyte is used as a cathode electrode, and peroxide Provided is an air electrode characterized by comprising a dipole electric double layer formed of hydrogen.
次いで、本発明は過酸化水素を含み、電気二重層を電極との界面に形成する中性又はアルカリ性水性電解液と、該電解液中に浸漬する金属銅又はその合金からなるカソード電極と、カソード電極より電極電位が卑なる金属又はその合金からなるアノード電極とを備え、カソード電極と電解液との界面の間に形成される過酸化水素を含む電解液により双極子電気二重層を形成し、炭素電極に代え、空気極として使用できる金属空気電池を提供するものである。 Next, the present invention includes a neutral or alkaline aqueous electrolyte containing hydrogen peroxide and forming an electric double layer at the interface with the electrode, a cathode electrode made of metallic copper or an alloy thereof immersed in the electrolyte, and a cathode An anode electrode made of a metal or an alloy thereof whose electrode potential is less noble than that of the electrode, and an electrolyte solution containing hydrogen peroxide formed between the interface between the cathode electrode and the electrolyte solution to form a dipole electric double layer, A metal-air battery that can be used as an air electrode instead of a carbon electrode is provided.
本発明によれば、電解液中の過酸化水素は電気双極子（ダイポール）であるから電極表面に配向して双極子電気二重層を形成する。図４Ａ及びＢはその機能説明図である。図中、電解液がアノード電極とカソード電極との間に介在すると、両電極には通常、電解液との界面に電気二重層が形成されるが、本発明では特に電解液中に過酸化水素が追加添加されているので、その双極子（ダイポール）としての機能により双極子電気二重層を形成する。その要因の一つは過酸化水素の双極子としての機能である。電極表面との界面には電気双極子（ダイポール）の配列によって、双極子電気二重層が形成される。その上、しかも過酸化水素の酸化力も協働し、本発明によれば、金属空気電池のボトルネックとなっているアノード側負極に比べてカソード側正極のイオン化進行速度が劣る原因を過酸化水素の添加によって改善することができる（なお、過酸化水素の添加は酸性電解液のボルタ電池における水素イオンによる影響を回避する減極剤の作用と異なる）が、電解液に添加した過酸化水素は双極子電気二重層を形成するだけでなく、銅カソードに空気極としての触媒機能を持たせ、銅カソード電極表面で種々の発電反応を発揮する。 According to the present invention, since the hydrogen peroxide in the electrolyte is an electric dipole (dipole), it is oriented on the electrode surface to form a dipole electric double layer. 4A and 4B are functional explanatory diagrams thereof. In the figure, when the electrolyte intervenes between the anode electrode and the cathode electrode, an electric double layer is usually formed at the interface between the electrodes and the electrolyte. is additionally added, it functions as a dipole to form a dipole electric double layer. One of the factors is the function of hydrogen peroxide as a dipole. A dipole electric double layer is formed at the interface with the electrode surface by the arrangement of electric dipoles (dipoles). In addition, the oxidizing power of hydrogen peroxide also cooperates, and according to the present invention, hydrogen peroxide is the cause of the inferior ionization progress rate of the positive electrode on the cathode side compared to the negative electrode on the anode side, which is the bottleneck of the metal-air battery. (Note that the addition of hydrogen peroxide is different from the action of a depolarizer that avoids the effects of hydrogen ions in a voltaic battery with an acidic electrolyte), but the hydrogen peroxide added to the electrolyte is In addition to forming a dipole electric double layer, the copper cathode has a catalytic function as an air electrode, and various power generation reactions are exhibited on the surface of the copper cathode electrode.
過酸化水素を供給した、空気電池ではアノードでは２Ｍｇ→２Ｍｇ２＋＋４e-と酸化反応で電子を得る一方、カソード電極ではＯ２＋２Ｈ２Ｏ+４e-→４ＯＨ―と酸素は還元され、ヒドロキシイオンを生成して発電するが、過酸化水素を含む中性又はアルカリ性電解液中でカソード電極として銅電極を使用すると、その電流量は増大していった。この要因をみると、かかる構成の電池では、金属空気電池のネックとなっているイオン化反応遅延が過酸化水素の添加により解消するだけでなく、カソード側での、酸素と水素の発生を確認できるため、銅電極表面では過酸化水素が分解する燃料電池反応を起こしていると考えられる。通常、過酸化水素燃料電池では非特許文献１に示すように、酸性領域では
カソード: Ｈ２Ｏ２+ ２Ｈ＋+ ２e-→ ２Ｈ２Ｏ (1.78 V対NHE)(1)
アノード: Ｈ２Ｏ２→ Ｏ２+ ２Ｈ＋+ ２e-　(0.682 V対NHE)(2)
合計: ２Ｈ２Ｏ２→ ２Ｈ２Ｏ + Ｏ２　(1.09 V)(3)の電気化学反応を起こしているが、
過酸化水素を添加してなる本発明の中性又はアルカリ性領域では、
カソード: Ｈ２Ｏ２+ ２Ｈ＋+２ＯＨ-＋２e-→ ２Ｈ２Ｏ+２ＯＨ- (1)
アノード: Ｈ２Ｏ２+２ＯＨ-→ Ｏ２+ ２Ｈ＋+２ＯＨ－+ ２e-(2)
の電気化学反応を起こしているものと考えられ、
さらに本発明では過酸化水素を含む双極子電気二重層は銅カソード表面での触媒反応も伴って過酸化水素の分解による
２Ｈ２Ｏ２→ ・４ＯＨ→　２Ｏ２+　２Ｈ２　+ ４e-　の発電反応
又は　ヒドロキシイオンの分解による４ＯＨ-→Ｏ２＋２Ｈ２Ｏ+４e-の発電反応が伴うと思われる。 In the air battery supplied with hydrogen peroxide, the anode obtains electrons through an oxidation reaction of 2Mg→2Mg 2+ +4e − , while the cathode electrode reduces oxygen to O 2 +2H 2 O+4e − →4OH − to form hydroxy ions. It generated and generated electricity, and the amount of current increased when a copper electrode was used as the cathode electrode in a neutral or alkaline electrolyte containing hydrogen peroxide. Looking at this factor, in a battery with such a configuration, not only is the ionization reaction delay, which is a bottleneck in metal-air batteries, eliminated by the addition of hydrogen peroxide, but it is also possible to confirm the generation of oxygen and hydrogen on the cathode side. Therefore, it is considered that the hydrogen peroxide decomposes in the fuel cell on the surface of the copper electrode. Normally, in the acidic region, the cathode: H 2 O 2 + 2H ++ 2e − → 2H 2 O (1.78 V vs. NHE) (1)
Anode: H 2 O 2 →O 2 + 2H ++ 2e − (0.682 V vs NHE) (2)
Total: 2H 2 O 2 → 2H 2 O + O 2 (1.09 V)(3) electrochemical reaction,
In the neutral or alkaline region of the present invention by adding hydrogen peroxide,
Cathode: H 2 O 2 + 2H + +2OH - +2e - → 2H 2 O+2OH - (1)
Anode: H 2 O 2 +2OH - → O 2 + 2H + +2OH - + 2e - (2)
It is thought that the electrochemical reaction of
Furthermore, in the present invention, the dipole electric double layer containing hydrogen peroxide is accompanied by a catalytic reaction on the surface of the copper cathode, and a power generation reaction of 2H 2 O 2 → .4OH → 2O 2 + 2H 2 + 4e - due to the decomposition of hydrogen peroxide. Or, it is thought to be accompanied by a power generation reaction of 4OH − →O 2 +2H 2 O+4e− due to decomposition of hydroxy ions.
本発明の金属空気電池を示す概念図である。1 is a conceptual diagram showing a metal-air battery of the present invention; FIG. スペーサを介した銅カソード電極を示す斜視図である。FIG. 4 is a perspective view showing a copper cathode electrode with spacers interposed therebetween; 銅カソード電極とマグネシウムアノード電極を組み合わせた状態の側面概念図である。FIG. 3 is a conceptual side view of a state in which a copper cathode electrode and a magnesium anode electrode are combined; 多数のマイクロキャパシタを形成する銅カソード電極の写真である。1 is a photograph of copper cathode electrodes forming a number of microcapacitors. 図３Ａの銅カソード電極とマグネシウムアノード電極を組み合わせた状態の側面概念図である。FIG. 3B is a schematic side view of a state in which the copper cathode electrode and the magnesium anode electrode of FIG. 3A are combined; 本発明の空気極のキャパシタの構成を示す概念図で、（Ａ）はアノード及びカソード電極表面に過酸化水素双極子と金属酸化物とを含む電気二重層が形成されている状態を、（Ｂ）はアノード電極表面のみに過酸化水素双極子と金属酸化物とを含む電気二重層が形成されている状態を示す。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a conceptual diagram showing the configuration of the air electrode capacitor of the present invention, in which (A) shows a state in which an electric double layer containing hydrogen peroxide dipoles and a metal oxide is formed on the surfaces of the anode and cathode electrodes; ) shows a state in which an electric double layer containing hydrogen peroxide dipoles and a metal oxide is formed only on the surface of the anode electrode. 本発明のマイクロキャパシタを電気二重層として備える構成を示す概念図（Ａ）及び（Ｂ）である。1A and 1B are conceptual diagrams showing a configuration having a microcapacitor of the present invention as an electric double layer; FIG.
（金属空気電池の構成）
本発明では、図１に示すように、Ａｌ又はＭｇアノード電極とＣｕカソード電極を過酸化水素を含む中性又はアルカリ性電解液に浸漬して対向配置して金属空気電池を構成してなる。
アノード電極／過酸化水素を含むアルカリ性電解液／カソード電極の構成における起電力であって、その金属空気電池の反応は次の通りである。
アノード側の金属酸化反応をＭ→Ｍｎ＋　+　ｎｅ-と、
他方、カソード側の酸素還元反応をＯ２＋Ｈ２Ｏ＋４ｅ-→４ＯＨ-　となる。
本発明では、金属空気電池のカソード側の還元反応を促進するために、電解液に過酸化水素を添加し、アノード側負極に比べてカソード側正極のイオン化進行速度が劣る原因を改善した。
すなわち、金属銅はＣu＋2Ｈ２Ｏ２→Ｃu２＋＋2ＯＨ＋2ＯＨ-及び
Ｃu＋2ＯＨ→Ｃu２＋＋2ＯＨ-と一部過酸化水素に溶けるが、Ｃu２＋＋2ＨＯ２ -→Ｃｕ＋2ＨＯ２と、ＨＯ２基がHaber u.　Willstatter連鎖によって過酸化水素の分解を促進するからであると思われる（非特許文献３）。 (Structure of metal-air battery)
In the present invention, as shown in FIG. 1, an Al or Mg anode electrode and a Cu cathode electrode are immersed in a neutral or alkaline electrolyte containing hydrogen peroxide and placed opposite each other to form a metal-air battery.
Electromotive force in the configuration of anode electrode/alkaline electrolyte containing hydrogen peroxide/cathode electrode, the reaction of the metal-air battery is as follows.
The metal oxidation reaction on the anode side is M → M n + + ne - ,
On the other hand, the oxygen reduction reaction on the cathode side becomes O 2 +H 2 O+4e − →4OH − .
In the present invention, hydrogen peroxide is added to the electrolytic solution in order to promote the reduction reaction on the cathode side of the metal-air battery, thereby improving the cause of the inferior ionization rate of the positive electrode on the cathode side compared to the negative electrode on the anode side.
That is, metallic copper dissolves partially in hydrogen peroxide as Cu+2H 2 O 2 →Cu 2+ +2OH+2OH - and Cu+2OH → Cu 2+ +2OH - , but Cu 2+ +2HO 2 - →Cu+2HO 2 and HO 2 groups form the Haber u. Willstatter chain. This is thought to be because the decomposition of hydrogen peroxide is accelerated by (Non-Patent Document 3).
さらに、本発明においては、カソード側から水素と酸素ガスの発生が認められるので、通常の過酸化水素燃料電池（非特許文献１参照）を構成するだけでなく、
カソード: Ｈ２Ｏ２+ ２Ｈ＋ + ２e-→ ２Ｈ２Ｏ (1.78 V対NHE)(1)
アノード: Ｈ２Ｏ２→ Ｏ２+ ２Ｈ＋ + ２e-　(0.682 V対NHE)(2)
合計: ２Ｈ２Ｏ２→ ２Ｈ２Ｏ + Ｏ２　(1.09 V)(3)
本発明では銅カソード表面での触媒反応も伴って過酸化水素２Ｈ２Ｏ２→・４ＯＨ　に分解して、・４ＯＨ　⇒Ｈ２+Ｏ２＋４ｅ-↑と酸素と水素を発生させるか又はヒドロキシイオン４ＯＨ-　⇒Ｈ２+Ｏ２＋４ｅ-を分解して酸素と水素を発生させ、同時に電子を放出するものと思われる。 Furthermore, in the present invention, since hydrogen and oxygen gas are generated from the cathode side, it is possible not only to constitute a normal hydrogen peroxide fuel cell (see Non-Patent Document 1),
Cathode: H 2 O 2 + 2H + + 2e − → 2H 2 O (1.78 V vs NHE) (1)
Anode: H 2 O 2 →O 2 + 2H ++ 2e − (0.682 V vs NHE) (2)
Total: 2H2O2 → 2H2O + O2 ( 1.09 V)(3)
In the present invention, hydrogen peroxide 2H 2 O 2 →.4OH is accompanied by a catalytic reaction on the copper cathode surface.　4OH　⇒H 2 +O 2 +4e − ↑ and oxygen and hydrogen are generated, or the hydroxyl ion 4OH − ⇒H 2 +O 2 +4e − is decomposed to generate oxygen and hydrogen, and electrons are released at the same time. .
図1は、本発明の金属空気電池の概念図である。Ｍｇアノード電極とＣｕカソード電極と電解液の間に過酸化水素を含む電解液が介在すると、電解液と電極との界面には過酸化水素を双極子とする電気二重層が形成される一方、過酸化水素により電極表面の双方（図４Ａ）又は少なくともアノード側（図４Ｂ）に過酸化水素で酸化された金属イオンの酸化物が介在する結果、両電極は短絡せず、これらが協働してキャパシタ機能を発揮する。過酸化水素は双極子としてカソード電極表面に双極子電気二重層を形成するが、同時に、電解液中で電極、アノード電極を構成する典型金属のマグネシウム、アルミニウム、亜鉛は電解液との反応性が高く、特にアノード金属イオンを酸化して酸化物（一部は金属水酸化物）を形成するため、アノード電極とカソード電極が接触しても短絡せず、電極をセパレートすることが分かる（図２Ａ及びＢ、図４Ａ及びＢ）。 FIG. 1 is a conceptual diagram of the metal-air battery of the present invention. When an electrolytic solution containing hydrogen peroxide is interposed between the Mg anode electrode, the Cu cathode electrode, and the electrolytic solution, an electric double layer having hydrogen peroxide as a dipole is formed at the interface between the electrolytic solution and the electrode, As a result of hydrogen peroxide interposing oxides of hydrogen peroxide-oxidized metal ions on both electrode surfaces (Fig. 4A) or at least on the anode side (Fig. 4B), the electrodes do not short and they work together. function as a capacitor. Hydrogen peroxide forms a dipole electric double layer on the surface of the cathode electrode as a dipole. In particular, the anode metal ions are oxidized to form oxides (some of which are metal hydroxides). and B, FIGS. 4A and B).
本発明においては、カソード電極表面に絶縁性電気二重層を形成する酸化剤として電解液に過酸化水素を添加したが、金属表面を酸化する各種酸化剤であって、電気二重層を形成する機能を有する限り、過酸化水素とともに使用して同様の機能と作用効果を奏することができることは当業者であれば、本明細書の記載から理解できる。 In the present invention, hydrogen peroxide was added to the electrolytic solution as an oxidizing agent for forming an insulating electric double layer on the surface of the cathode electrode. A person skilled in the art can understand from the description of this specification that the same function and effect can be achieved by using with hydrogen peroxide as long as it has
本発明においては、前記水溶性電解液に過酸化水素の一部又は全部を過炭酸ナトリウムにより供給するのが好ましい。具体的には、０．５から２．０モルのアルカリ金属又はアルカリ土類金属ハロゲン化塩、特に塩化ナトリウムを含む中性又はアルカリ性水溶液に対し数％から十数％の過酸化水素水(体積％)又は過炭酸ナトリウム(重量％)を添加するのが好ましい。 In the present invention, it is preferable that sodium percarbonate is used to supply part or all of the hydrogen peroxide to the aqueous electrolytic solution. Specifically, a neutral or alkaline aqueous solution containing 0.5 to 2.0 mol of alkali metal or alkaline earth metal halide salt, particularly sodium chloride, and several percent to ten and several percent of hydrogen peroxide water (volume %) or sodium percarbonate (% by weight) is preferably added.
前記アノード電極とカソード電極とを交互にスペーサを介して一定の間隔をもって対向配置し、アノード電極とカソード電極との接触部に過酸化水素を含む水溶性電解液により電気二重層キャパシタを形成する（図４Ａ及びＢ）が、前記スペーサがカソード電極と同じ金属銅又は銅合金からなり、対極表面に一定間隔を隔てる点状突起を有する（図５Ａ及びＢ）のが好ましい。 The anode electrode and the cathode electrode are alternately arranged to face each other with a constant spacing interposed between them, and an electric double layer capacitor is formed from an aqueous electrolyte solution containing hydrogen peroxide at the contact portion between the anode electrode and the cathode electrode ( 4A and B), the spacer is preferably made of the same metallic copper or copper alloy as the cathode electrode and has point-like projections at regular intervals on the counter electrode surface (FIGS. 5A and B).
（性能比較）
図２Ａ及びＢ及び図３Ａ及びＢに示す銅電極を使用して図５Ａ及びＢに示す概念のマイクロキャパシタがある場合とない場合の電池の性能を比較した。
容量３０００ｍｌの上方開放型直方体プラスチック容器を用いる。図５Ａ及びＢでは、１ｍｍ厚み、縦横１００×１００ｍｍの銅カソード電極板１０に上下左右に１５０ｍｍないし２００ｍｍ間隔で多数の三角形の５０ｍｍの高さの突起１１を切り立て（写真図３Ａ）、図３Bに示すように、両端は銅板１０は突起１１を内向きに、真ん中は背中合わせに張り合わせた銅電極１０で２ｍｍ厚み、縦横１００×１００ｍｍのマグネシウムアノード電極板２０を挟み込んで組み合わせる。
この組み合わせ電極を使うと図５Ａ及びＢに示すように、銅カソード電極の表面にマイクロコンデンサを形成することができる。
他方、図２Ａに示す、１ｍｍ厚み、縦横１００×１００ｍｍの銅カソード電極板１０に銅電極板をＴ字形に切り出し、端部を折り曲げて形成したスペーサＳを取り付ける。このカソード電極板でスペーサＳを介して２ｍｍ厚みの縦横１００×１００ｍｍのＭｇアノード電極板２０の両側を挟みつける。３枚の銅カソード電極板１０で、２枚のＭｇアノード電極板２０はスペーサＳを介して交互に挟みつけると、図２Ｂに示す上部端面図の状態となる。この組み合わせ電極を使うと図４Ａ及びＢに示すマイクロコンデンサを形成しない。 (performance comparison)
The copper electrodes shown in FIGS. 2A-B and 3A-B were used to compare the performance of cells with and without the microcapacitor concept shown in FIGS. 5A-B.
A top-opening cuboid plastic container with a capacity of 3000 ml is used. 5A and B, a large number of triangular protrusions 11 with a height of 50 mm were cut vertically and horizontally at intervals of 150 mm to 200 mm on a copper cathode electrode plate 10 having a thickness of 1 mm and a size of 100 mm by 100 mm (photograph FIG. 3A), and FIG. 3B. As shown in FIG. 2, the copper plates 10 at both ends are laminated with the protrusions 11 facing inward, and the copper electrodes 10 are laminated back to back in the middle to sandwich a magnesium anode electrode plate 20 having a thickness of 2 mm and a length and width of 100×100 mm.
This combination of electrodes can be used to form a microcapacitor on the surface of the copper cathode electrode, as shown in FIGS. 5A and B. FIG.
On the other hand, a copper cathode electrode plate 10 having a thickness of 1 mm and a length and width of 100×100 mm shown in FIG. A Mg anode electrode plate 20 having a thickness of 2 mm and a size of 100×100 mm is sandwiched between the cathode electrode plates with spacers S interposed therebetween. When the three copper cathode electrode plates 10 and the two Mg anode electrode plates 20 are alternately sandwiched with the spacer S interposed therebetween, the top end view shown in FIG. 2B is obtained. Using this combination of electrodes does not form the microcapacitor shown in FIGS.
プラスチック容器にはおよそ１５００ｍｌの純水に塩化ナトリウム０．５モル／ｌ以上、好ましくは１．５モル／ｌ以上２モル／ｌの電解液を調整し、これに過炭酸ナトリウム５０～１００ｇと３０％過酸化水素水５０ｍｌを加える。電池反応は一定時間過ぎると、過酸化水素が消費され、電球が減少するので、２～３時間ごとに１０ｍｌの３０％過酸化水素水を添加する。 In a plastic container, an electrolytic solution of 0.5 mol/l or more, preferably 1.5 mol/l or more, 2 mol/l of sodium chloride is prepared in about 1500 ml of pure water, and 50 to 100 g of sodium percarbonate and 30 g of sodium percarbonate are added thereto. 50 ml of % hydrogen peroxide solution is added. After a certain period of time, the cell reaction consumes hydrogen peroxide and the light bulb decreases, so add 10 ml of 30% hydrogen peroxide solution every 2 to 3 hours.
本件実施例においては、図２ＡおよびＢの電極構成と図３ＡおよびＢの電極構成の性能を比較してマイクロキャパシタを銅カソード電極表面に形成する場合とない場合の性能比較を行った。
電極構成以外は同じ条件としたので、アルカリ電解水における過酸化水素燃料電池反応に、マグネシウム空気電池反応が伴うものである点は同じである。したがって、以下の反応式に基づき、
過酸化水素がＨ２Ｏ２＋２Ｈ２Ｏ＋２ｅ-→２Ｈ２Ｏ＋２ＯＨ-に分解する一方、カソード電極側でＨ２Ｏ２+２ＯＨ-→Ｏ２＋２Ｈ２Ｏ＋２ｅ-の酸化反応を起こすだけでなく、アルカリ性電解液での金属酸化反応がＭｇ→Ｍｇ２＋＋２ｅ-となり、カソード側での酸素を還元してイオン化する反応がＯ２＋２Ｈ２Ｏ＋４ｅ-→４ＯＨ-と典型的な金属空気電池反応が起こる。但し、過酸化水素燃料電池及び金属空気電池反応では酸素ガスは発生すると理解できるが、上記構成では酸素ガスだけでなく、水素ガスも発生する。ということは、非特許文献３（水渡英二著、物理化学の進歩（１９３６）、１０（３）：１５４～１６５頁）に示唆されるように、銅カソード電極表面で触媒機能が働き、過酸化水素の分解又はヒドロキシイオンの分解が起こり、発電反応に繋がっていると思われる。
２Ｈ２Ｏ２→４・ＯＨ→Ｈ２＋Ｏ２＋４e-
４ＯＨ-→Ｈ２＋Ｏ２＋４e- In this example, the performance of the electrode configuration of FIGS. 2A and B was compared with the electrode configuration of FIGS. 3A and B to compare the performance with and without the microcapacitor formed on the copper cathode electrode surface.
Since the conditions were the same except for the electrode configuration, the point that the hydrogen peroxide fuel cell reaction in alkaline electrolyzed water was accompanied by the magnesium air cell reaction was the same. Therefore, based on the following reaction equation,
While hydrogen peroxide decomposes into H 2 O 2 +2H 2 O+2e − →2H 2 O+2OH − , it not only causes an oxidation reaction of H 2 O 2 +2OH − →O 2 +2H 2 O+2e − on the cathode electrode side, but also is alkaline. A typical metal-air battery reaction occurs in which the metal oxidation reaction in the electrolyte becomes Mg→Mg 2+ +2e − , and the oxygen reduction and ionization reaction on the cathode side becomes O 2 +2H 2 O+4e − →4OH − . However, although it can be understood that oxygen gas is generated in the hydrogen peroxide fuel cell and the metal-air cell reaction, not only oxygen gas but also hydrogen gas is generated in the above configuration. That is, as suggested in Non-Patent Document 3 (Eiji Mizuwatari, Advances in Physical Chemistry (1936), 10(3): pp. 154-165), a catalytic function acts on the surface of the copper cathode electrode, and overheating occurs. It is believed that decomposition of hydrogen oxide or decomposition of hydroxy ions occurs, leading to a power generation reaction.
2H2O2-> 4.OH- >H2 + O2 + 4e-
4OH − →H 2 +O 2 +4e −
以上、本発明を一対の電極として、Ｍgアノード電極とＣuカソード電極とを用いて説明したが、同種の典型金属から選はれるアルミニウム及び亜鉛並びにその合金を用いても電極電位差は異なるものの、同種の効果が得られることは言うまでもない。 As described above, the present invention has been described using an Mg anode electrode and a Cu cathode electrode as a pair of electrodes. It goes without saying that the effect of

Claims (6)

  1. 中性又はアルカリ性電解液と、空気極と、空気極より電極電位が卑なるアルミ、亜鉛、マグネシウム及びその合金から選ばれる典型金属をアノードとする電極とを備える金属空気電池において、前記電解液が過酸化水素を含む一方、前記空気極が銅及びその合金から選ばれる遷移金属からなり、銅及びその合金からなる電極と過酸化水素を含む電解液との界面に、過酸化水素を双極子とする電気二重層を形成してなる、ことを特徴とする空気極。 A metal-air battery comprising a neutral or alkaline electrolyte, an air electrode, and an electrode whose anode is a typical metal selected from aluminum, zinc, magnesium, and alloys thereof whose electrode potential is less noble than that of the air electrode, wherein the electrolyte is While containing hydrogen peroxide, the air electrode is made of a transition metal selected from copper and its alloys, and hydrogen peroxide is formed as a dipole at the interface between the electrode made of copper and its alloys and the electrolyte containing hydrogen peroxide. An air electrode characterized by forming an electric double layer that
  2. 中性又はアルカリ性電解液と、空気極と、空気極より電極電位が卑なるアルミ、亜鉛、マグネシウム及びその合金から選ばれる典型金属をアノードとする電極とを備える金属空気電池であって、前記電解液が過酸化水素を含む一方、前記空気極が銅及びその合金から選ばれる遷移金属から選ばれ、前記銅及びその合金から選ばれる遷移金属からなる電極と電解液との界面に、過酸化水素を双極子とする電気二重層を形成し、空気極として作用させることを特徴とする金属空気電池。 A metal-air battery comprising a neutral or alkaline electrolyte, an air electrode, and an electrode whose anode is a typical metal selected from aluminum, zinc, magnesium, and alloys thereof whose electrode potential is less noble than that of the air electrode, wherein the electrolysis While the liquid contains hydrogen peroxide, the air electrode is selected from transition metals selected from copper and its alloys, and hydrogen peroxide is added to the interface between the electrode made of the transition metal selected from the copper and its alloys and the electrolyte. A metal-air battery characterized by forming an electric double layer with a dipole and acting as an air electrode.
  3. 　前記電解液が過酸化水素供給源として過炭酸ナトリウム及び/又は過酸化水素水を含む一方、電解液がアルカリ金属又はアルカリ土類金属ハロゲン化物から選ばれる電解質を含む請求項２記載の金属空気電池。 3. The metal-air battery according to claim 2, wherein the electrolyte contains sodium percarbonate and/or hydrogen peroxide solution as a hydrogen peroxide supply source, and the electrolyte contains an electrolyte selected from alkali metal or alkaline earth metal halides. .
  4. 前記アノード電極と空気極とが導電性金属スペーサを介してイオン流動を確保する一定の間隔をもって対向配置してなる電極構造を１組以上有する請求項２記載の金属空気電池。 3. The metal-air battery according to claim 2, comprising at least one set of electrode structures in which said anode electrode and said air electrode are arranged opposite to each other with a constant gap for ensuring ion flow via a conductive metal spacer.
  5. 前記スペーサが空気極と同じ金属銅又は銅合金からなり、空気極が対極となるアノード電極表面に一定間隔を隔てて分布する点状接触部を有する請求項３記載の金属空気電池。 4. The metal-air battery according to claim 3, wherein said spacer is made of the same metallic copper or copper alloy as the air electrode, and the air electrode has point-like contact portions distributed at regular intervals on the surface of the anode electrode serving as a counter electrode.
  6. アノード側のアルカリ域での金属酸化反応がＭ→Ｍｎ＋＋ｎｅ-（但し、Ｍはマグネシウム、アルミニウム及び亜鉛から選ばれる典型金属、ｎは価数を示す）と、カソード側での酸素を還元してイオン化する反応がＯ２＋２Ｈ２Ｏ＋４ｅ-→４ＯＨ-からなる金属空気電池反応であって、
    アノード側でのアルカリ域での過酸化水素反応が
    Ｈ２Ｏ２＋２Ｈ２Ｏ＋２ｅ-→２Ｈ２Ｏ＋２ＯＨ-と、
    カソード側での反応が
    Ｈ２Ｏ２+２ＯＨ-→Ｏ２＋２Ｈ２Ｏ＋２ｅ-の酸化反応からなる過酸化水素反応を伴う請求項２記載の金属空気電池。     The metal oxidation reaction in the alkaline region on the anode side reduces M → M n+ +ne − (where M is a typical metal selected from magnesium, aluminum and zinc, and n indicates the valence) and oxygen on the cathode side. is a metal-air battery reaction consisting of O 2 + 2H 2 O + 4e - → 4OH - ,
    The hydrogen peroxide reaction in the alkaline region on the anode side is H 2 O 2 +2H 2 O+2e − →2H 2 O+2OH − ,
    3. The metal-air battery of claim 2 , wherein the reaction on the cathode side involves a hydrogen peroxide reaction consisting of an oxidation reaction of H2O2+2OH -- > O2 + 2H2O + 2e-.
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JP2014220107A (en) 2013-05-08 2014-11-20 株式会社ワイヤードジャパン Magnesium-air battery and method of manufacturing cathode thereof
JP2017092014A (en) * 2015-11-13 2017-05-25 基嗣 田島 Aluminum air battery
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